Herbicidal 2-(2-imidazolin-2-yl)fluoroalkoxy-, alkenyloxy- and alkynyloxy quinolines

ABSTRACT

The invention relates to novel difluoromethoxy-, trifluoromethoxy-, 1,1,2,2-tetrafluoroethoxy-, alkenyloxy- and alkynyloxypyridine and quinoline compounds and a method for controlling undesirable plant species therewith.

This is a division of application Ser. No. 702,098, filed Feb. 14, 1985,now U.S. Pat. No. 4,647,301, which is a continuation-in-part ofapplication Ser. No. 616,747, filed June 4, 1984 now abandoned, which isa continuation-in-part of Ser. No. 382,041, filed May 25, 1982 now U.S.Pat. No. 4,638,068; which is a continuation-in-part of abandoned Ser.No. 252,704, filed Apr. 9, 1981, which is a continuation-in-part of Ser.Nos. 155,909, 155,910, 155,867, 155,908, and 155,865 which were allfiled June 2, 1980 and are now abandoned.

SUMMARY OF THE INVENTION

The invention is difluoromethoxy-, trifluoromethoxy-,1,1,2,2-tetrafluoroethoxy-, alkenyloxy- and alkynyloxypyridine andquinoline compounds having the structures: ##STR1## wherein R₁ is C₁ -C₄alkyl;

R₂ is C₁ -C₄ alkyl or C₃ -C₆ cycloalkyl; and when R₁ and R₂ are takentogether with the carbon to which they are attached they may representC₃ -C₆ cycloalkyl optionally substituted with methyl;

R is hydrogen; ##STR2## C₁ -C₁₂ alkyl optionally substituted with one ofthe following groups: C₁ -C₃ alkoxy, halogen, hydroxy, C₃ -C₆cycloalkyl, benzyloxy, furyl, phenyl, halophenyl, loweralkylphenyl,loweralkoxyphenyl, nitrophenyl, carboxyl, loweralkoxycarbonyl, cyano ortriloweralkylammonium;

C₃ -C₁₂ alkenyl optionally substituted with one of the following groups:C₁ -C₃ alkoxy, phenyl, halogen or loweralkoxycarbonyl or with two C₁ -C₃alkoxy groups or two halogen groups;

C₃ -C₆ cycloalkyl optionally substituted with one or two C₁ -C₃ alkylgroups;

C₃ -C₁₀ alkynyl; or

a cation;

W is O or S;

X is hydrogen, halogen or methyl;

Y is hydrogen, halogen, C₁ -C₆ alkyl, C₁ -C₄ hydroxyloweralkyl, C₁ -C₆alkoxy, C₁ -C₄ alkylthio, phenoxy, C₁ -C₄ haloalkyl, nitro, cyano, C₁-C₄ alkylamino, di-C₁ -C₄ -loweralkylamino, C₁ -C₄ alkylsulfonyl orphenyl optionally substituted with one C₁ -C₄ alkyl, C₁ -C₄ alkoxy orhalogen, difluoromethoxy, trifluoromethoxy, 1,1,2,2-tetrafluoroethoxy,C₃ -C₈ straight or branched alkenyloxy optionally substituted with oneto three halogens, or C₃ -C₈ straight or branched alkynyloxy optionallysubstituted with one to three halogens;

Z is hydrogen, halogen, C₁ -C₆ alkyl, C₁ -C₄ hydroxyloweralkyl, C₁ -C₆alkoxy, C₁ -C₄ alkylthio, phenoxy, C₁ -C₄ haloalkyl, nitro, cyano, C₁-C₄ alkylamino, di-C₁ -C₄ -loweralkylamino, C₁ -C₄ alkylsulfonyl orphenyl optionally substituted with one C₁ -C₄ alkyl or C₁ -C₄ alkoxy orhalogen, C₃ -C₈ straight or branched alkenyloxy optionally substitutedwith one to three halogens, or C₃ -C₈ straight or branched alkynyloxyoptionally substituted with one to three halogens;

with the proviso that at least one of Y and Z is difluoromethoxy,trifluoromethoxy, 1,1,2,2-tetrafluoroethoxy, C₃ -C₈ straight or branchedalkenyloxy optionally substituted with one to three halogens, or C₃ -C₈straight or branched alkynyloxy optionally substituted with one to threehalogens;

L, M, Q and R₇ each represent hydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₄alkoxy, C₁ -C₄ alkylthio, C₁ -C₄ alkylsulfonyl, C₁ -C₄ haloalkyl,difluoromethoxy, trifluoromethoxy, 1,1,2,2-tetrafluoroethoxy, NO₂, CN,phenyl, phenoxy, amino, C₁ -C₄ alkylamino, diloweralkylamino,chlorophenyl, methylphenyl, phenoxy substituted with one Cl, CF₃, NO₂ orCH₃ group, C₃ -C₈ straight or branched alkenyloxy optionally substitutedwith one to three halogens, or C₃ -C₈ straight or branched alkynyloxyoptionally substituted with one to three halogens; with the proviso thatat least one of L, M, Q or R₇, is difluoromethoxy, trifluoromethoxy,1,1,2,2-tetrafluoroethoxy, C₃ -C₈ straight or branched alkenyloxyoptionally substituted with one to three halogens, or C₃ -C₈ straight orbranched alkynyloxy optionally substituted with one to three halogens;

the N-oxides thereof when W is O provided that R cannot be unsaturatedalkyl and Y or Z cannot be alkylamino, dialkylamino or alkylthio;

the optical isomers thereof when R₁ and R₂ are not the same;

the tautomers thereof;

the acid addition salts thereof except when R is a salt-forming cation.

In the above description of the compounds of the invention in thisapplication, when R is a cation, it is preferably an alkali metal,alkaline earth metals, manganese, copper, iron, zinc, cobalt, lead,silver, nickel, ammonium or organic ammonium.

The compounds of the present invention may be prepared by the proceduresdescribed in the pending application for U.S. Letters Patent of MarinusLos, Ser. No. 382,041, filed May 25, 1982, incorporated herein byreference thereto.

The substituted quinolines are prepared by starting with theappropriately substituted aniline and using the reactions previouslydescribed and shown in Flow Diagram I below. ##STR3##

The substituted pyridines are prepared by one or both of two methods. Inthe first case the product can be derived by alkylation of theappropriately substituted 5-pyridinol described in the pendingapplication. This is shown in Flow Diagram II below. ##STR4## where R₁₀is CF₂ H--, C₃ -C₈ straight or branched alkenyl or alkynyl optionallysubstituted with one to three halogens.

Alternatively the alkenyloxy or alkynyloxy group is introduced into themolecule prior to carboxylation as illustrated in Flow Diagram IIIbelow. ##STR5## where R₁₀ =C₃ -C₈ straight or branched alkenyl oralkynyl.

By yet another modification the trifluoromethoxy group can be introducedat an earlier stage of the synthetic sequence as shown in Flow DiagramIV below. ##STR6##

The starting material for the above sequence is described by E. J.Blanz, et al., J. Med. Chem., 13, 1124(1970). The method is described inthe above identified pending application.

The pyridine derivatives in which Z=alkenyl or alkynyl groups are mostreadily prepared by the displacement of the compounds in which Z=Cl bythe anion of the appropriate alcohol. This is shown in Flow Diagram Vbelow. ##STR7## in which R₁₀ is C₃ -C₈ straight or branched alkenyl oralkynyl optionally substituted with one to three halogens. Cyclizationof the appropriate acid with dicyclohexylcarbodiimide gives the3,5-dione as shown in Flow Diagram VI below. ##STR8##

When the cyclization is carried out in acetic anhydride, the otherisomer, the 2,5-dione, is obtained as shown in the Flow Diagram VIIbelow. ##STR9##

The preparation of the N-oxides can be accomplished as shown in FlowDiagram VIII below. ##STR10## In order to prepare the compounds whereZ=alkenyloxy or alkynyloxy, the chloro derivative is converted to itsN-oxide as shown below and the chlorine then displaced by theappropriate alkenyl or alkynyl alkoxide followed by acid hydrolysis asillustrated in Flow Diagram IX below. ##STR11##

The difluoromethoxy-, trifluoromethoxy-, 1,1,2,2-tetrafluoroethoxy-,alkenyloxy-, and alkynyloxypyridine and quinoline compounds of theinvention are exceedingly effective herbicidal agents useful for thecontrol of an exceptionally wide variety of herbaceous and woody annualand perennial monocotyledonous and dicotyledonous plants. Moreover,these compounds are herbicidally effective for controlling weedsindigenous to both dry land and wet land and are unique in theireffectiveness in controlling the above-said plants when applied to thefoliage thereof or to soil or water containing seeds or otherpropagating organs of said plants such as tubers, rhizomes or stolons,at rates of from about 0.016 to 4.0 kg/ha, and preferably at rates fromabout 0.032 to 2.0 kg/ha.

Additionally, it has been found that some of the compounds of theinvention are selective herbicides when applied to the foliage of plantsor to soil containing seeds of said plants at relatively low rates ofapplication, i.e., at from 0.016 to about 2.0 kg per hectare, dependingon the compound used and crop treated, and that certain compounds areeffective for increasing branching of leguminous crops and effectingearly maturation of grains.

It is, of course, obvious that rates of application above the 4.0 kg/halevel can also be used to effectively kill undesirable plant species;however, rates of application of toxicant above the level necessary tokill the undesirable plants should be avoided since application ofexcessive amounts of toxicant is costly and serves no useful function inthe environment.

Among the plants which may be controlled with the compounds of thisinvention are: Elatine triandra, Sagittaria pygmaea, Scirpus hotarui,Cyperus serotinus, Eclipta alba, Cyperus difformis, Rotala indica,Lindernia pyridoria, Echinochloa crus-galli, Digitaria sanguinalis,Setaria viridis, Cyperus rotundus, Convolvulus arvensis, Agropyronrepens, Datura stramonium, Alopecurus myosuroides, Ipomoea spp., Sidasponosa, Ambrosia artemisiifolia, Eichhornia crassipes, Xanthiumpensylvanicum, Sesbania exalta, Avena fatua, Abutilon theophrasti,Bromus tectorum, Sorghum halepense, Lolium spp., Panicumdichotomiflorum, Matricaria spp., Amaranthus retroflexus, Cirsiumarvense and Rumex japonicus.

Since the difluoromethoxy-, trifluoromethoxy-,(1,1,2,2-tetrafluoroethoxy)-, alkenyloxy-, and alkynyloxypyridine andquinoline derivatives, wherein R₃ is a salt-forming cation, are watersoluble, these compounds can simply be dispersed in water and applied asa dilute aqueous spray to the foliage of plants or to soil containingpropagating organs thereof. These salts also lend themselves toformulation as flowable concentrates.

Wettable powders can be prepared by grinding together about 20 to 45% byweight of a finely divided carrier such as kaolin, bentonite,diatomaceous earth, attapulgite, or the like, 45 to 80% by weight of theactive compound, 2 to 5% by weight of a dispersing agent such as sodiumlignosulfonate, and 2 to 5% by weight of a nonionic surfactant, such asoctylphenoxy polyethoxy ethanol, nonylphenoxy polyethoxy ethanol or thelike.

A typical flowable liquid can be prepared by admixing about 40% byweight of the active ingredient with about 2% by weight of a gellingagent such as bentonite, 3% by weight of a dispersing agent such assodium lignosulfonate, 1% by weight of polyethylene glycol and 54% byweight of water.

A typical emulsifiable concentrate can be prepared by dissolving about 5to 25% by weight of the active ingredient in about 65 to 90% by weightof N-methylpyrrolidone, isophorone, butyl cellosolve, methylacetate orthe like and dispersing therein about 5 to 10% by weight of a nonionicsurfactant such as an alkylphenoxy polyethoxy alcohol. This concentrateis dispersed in water for application as a liquid spray.

When the compounds of the invention are to be used as herbicides wheresoil treatments are involved, the compounds may be prepared and appliedas granular products. Preparation of the granular product can beachieved by dissolving the active compound in a solvent such asmethylene chloride, N-methylpyrrolidone or the like and spraying thethus-prepared solution on a granular carrier such as corncob grits,sand, attapulgite, kaolin or the like.

The granular product thus prepared generally comprises about 3 to 20% byweight of the active ingredient and about 97 to 80% by weight of thegranular carrier.

In order to facilitate a further understanding of the invention, thefollowing examples are presented primarily for the purpose ofillustrating certain more specific details thereof. The invention is notto be deemed limited thereby except as defined in the claims. Unlessotherwise noted, all parts are by weight.

EXAMPLE 1 Preparation of2-(5-hydroxy-2-pyridyl)-4-isopropyl-4-methyl-2-imidazolin-5-one##STR12##

To a stirred suspension of 13.9 g 5-hydroxy-2-pyridinecarboxylic acid in200 mL THF containing 31 mL of triethylamine at -10° C. is added 19.1 mLethyl chloroformate. An additional 100 mL THF is added to the thickmixture. After ten minutes, a solution containing 13.4 g2-amino-2,3-dimethylbutyramide in 50 mL THF is added dropwise. Themixture is stirred for two hours at room temperature, about 60 mL wateradded, and the mixture filtered and the THF removed in vacuo. Theresidue is extracted with ethyl acetate, the organic phase washed withbrine, dried and concentrated to leave a thick orange oil.

The oil is dissolved in 95 mL of 5N NaOH and heated with stirring forthree hours at 65° C. After cooling to 0° C., acetic acid is added toneutralize the base and the precipitate removed by filtration. Thissolid is slurried in cold methanol to give 15.2 g2-(5-hydroxy-2-pyridyl)-4-isopropyl-4-methyl-2-imidazolin-5-one, mp252°-254° C.

EXAMPLE 2 Preparation of5-hydroxy-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinic acid##STR13##

A mixture of containing 20 g of the hydroxypyridylimidazolinone, 16.7 gt-butyldimethylchlorosilane and 15.65 g imidazole in 200 mL DMF isstirred at 50° C. for 16 hours. The mixture is cooled, poured into 400mL of a saturated sodium sulfate solution and extracted with 4×250 mLether. The combined extracts are washed with water and brine, dried andconcentrated. Trituration with ether-hexane gives 1.3 g startingmaterial. The filtrate is concentrated and the residue dissolved inether. The ether solution is then washed with water, dried andconcentrated to give 13.8 g crystalline residue of thet-butyldimethylsilyl ether intermediate.

To the silyl ether in 300 mL THF is added dropwise under nitrogen at-70° C. with stirring 91 mL of a 0.9M solution of butyl lithium inhexane. After stirring for two and one-half hours, excess fresh solidcarbon dioxide is added and stirring continued at -70° C. for one hour.The mixture is stirred at room temperature for 17 hours. The THF isremoved in vacuo and the residue dissolved in 300 mL water, filtered andthe filtrate extracted with 3×100 mL methylene chloride. The extractsare discarded. The pH of the aqueous phase is adjusted to 3 andextracted into methylene chloride, and the organic phase separated,dried, and concentrated to give the desired title product. A largerquantity crystallized from the remaining aqueous phase to give5-hydroxy-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinicacid. A pure sample has mp 255°-257° C.

EXAMPLE 3 Preparation of5-hydroxy-2-(5-isopropyl-5-methyl-4-oxo-2-imidazolin-2-yl)nicotinate##STR14##

To a mixture containing 3.3 g acid and 2.05 g pyridine in 50 mLdimethoxyethane is added 3.72 g acetic anhydride and the mixture stirredovernight at room temperature under nitrogen.

The mixture is concentrated and the residue dissolved in xylene andconcentrated again. This is repeated. The residue is dissolved in drymethanol, the pH of the solution adjusted to 10 with sodium methoxideand the mixture stirred overnight under nitrogen at room temperature.The pH of the solution is adjusted to 5 with acetic acid, the mixtureconcentrated and the residue extracted with 2×50 mL hot ether. Theextracts are concentrated and the residue triturated with hexane to givethe product as a light yellow solid. This product can be recrystallizedfrom acetone-hexane to give analytically pure methyl5-hydroxy-2-(5-isopropyl-5-methyl-4-oxo-2-imidazolin-2-yl)nicotinate, mp200.5°-205° C.

Using essentially the same procedure but substituting the appropriateacid for the5-hydroxy-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinicacid, there is obtained the following methyl esters.

    ______________________________________                                         ##STR15##                                                                    R.sub.1                                                                            R.sub.2   Y           Z           mp °C.                          ______________________________________                                        CH.sub.3                                                                           CH(CH.sub.3).sub.2                                                                      H           OCH.sub.2CHCH.sub.2                                                                       117-                                                                          119                                    CH.sub.3                                                                           CH(CH.sub.3).sub.2                                                                      H           OCH.sub.2CCH                                       CH.sub.3                                                                           CH(CH.sub.3).sub.2                                                                      OCH.sub.2 CCH                                                                             H            83-84                                 CH.sub.3                                                                           CH(CH.sub.3).sub.2                                                                      OCH.sub.2 CCH.sub.2                                                                       H           103-                                                                          105                                    ______________________________________                                    

EXAMPLE 4 Preparation of methyl5-difluoromethoxy-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinate##STR16##

Into a solution containing 1.25 g methyl5-hydroxy-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-nicotinateand 1.40 g sodium methoxide in 50 mL absolute methanol at 50° C. ispassed through a dispersion tube, chlorodifluoromethane for one hour.The mixture is cooled to 5° C. and the pH adjusted to 5 with 2Nmethanolic HCl. The solution is filtered and the filtrate concentratedin vacuo. The residue is extracted with 2×100 mL ether, the extractscombined, dried and concentrated. The residue is chromatographed onsilica gel using ether as the eluant to give the product, analyticallypure methyl5-difluoromethoxy-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinateas a white crystalline solid, mp 104°-105° C.

Using essentially the same procedure but substituting the appropriatemethyl 5-hydroxy-2-(4,4-dialkyl 5-oxo-2-imidazolin-2-yl)nicotinate andusing either chlorodifluoromethane or tetrafluoroethylene, the compoundsare prepared.

    ______________________________________                                         ##STR17##                                                                    R.sub.1 R.sub.2    W        R'      mp °C.                             ______________________________________                                        CH.sub.3                                                                              CH(CH.sub.3).sub.2                                                                       O        CF.sub.2 CHF.sub.2                                                                    90-92                                     CH.sub.3                                                                              C.sub.2 H.sub.5                                                                          O        CHF.sub.2                                         CH.sub.3                                                                              Cyclopropyl                                                                              O        CHF.sub.2                                         ______________________________________                                    

EXAMPLE 5 Preparation of methyl2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-5-(2-propynyloxy)nicotinate##STR18##

To a stirred solution containing 3.5 g hydroxypyridine and 1.55 gpropargyl bromide in 100 mL THF under nitrogen is added 2.0 g DBU(1.8-diazabicyclo[5.4.0]undec-7-ene). The mixture is heated at 50°-55°C. for three hours, poured into water and extracted with 2×200 mL ether.The extract is dried and concentrated to give a crude product, which ischromatographed on silica gel. Elution with ether-hexane and pure ethergave the product which was recrystallized from ether-hexane to giveanalytically pure methyl2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-5-(2-propynyloxy)-nicotinate,mp 83°-84° C.

Utilizing essentially the same procedure but substituting theappropriate halide for propargyl bromide, the following compounds wereprepared.

    ______________________________________                                         ##STR19##                                                                    R.sub.1                                                                             R.sub.2   Y               Z   mp °C.                             ______________________________________                                        CH.sub.3                                                                            CH(CH.sub.3).sub.2                                                                      OCH.sub.2CHCH.sub.2                                                                           H   103-105                                   CH.sub.3                                                                            CH(CH.sub.3).sub.2                                                                       ##STR20##      H   105-107                                   CH.sub.3                                                                            CH(CH.sub.3).sub.2                                                                       ##STR21##      H     126-127.5                               CH.sub.3                                                                            C.sub.2 H.sub.5                                                                         OCH.sub.2CHCH.sub.2                                                                           H                                             CH.sub.3                                                                            CH(CH.sub.3).sub.2                                                                       ##STR22##      H                                             CH.sub.3                                                                            CH(CH.sub.3).sub.2                                                                       ##STR23##      H                                             CH.sub.3                                                                            CH(CH.sub.3).sub.2                                                                      OCH.sub.2 CHCHCH.sub.3                                                                        H   92-95                                     ______________________________________                                    

EXAMPLE 6 Preparation of5-(difluoromethoxy)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinicacid ##STR24##

To a solution containing 400 mg methyl ester in 20 mL methanol is added1.5 mL 2N NaOH and the mixture stirred at 40°-45° C. for two hours. ThepH of the solution is adjusted to 4 with 6N H₂ SO₄ and extracted twicewith 200 mL CH₂ Cl₂. The organic phases are combined, dried andconcentrated to give the product as a white powder. The5-(difluoromethoxy)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinicacid can be recrystallized from methylene chloride-hexane to giveanalytically pure material mp 184°-186° C.

Using essentially the same procedure but substituting the appropriatemethyl ester for the 5-difluoromethoxy derivative, there are preparedthe following acids:

    ______________________________________                                         ##STR25##                                                                    R.sub.1 R.sub.2    Y             mp °C.                                ______________________________________                                        CH.sub.3                                                                              CH(CH.sub.3).sub.2                                                                       OCH.sub.2CHCH.sub.2                                                                          98-101                                      CH.sub.3                                                                              CH(CH.sub.3).sub.2                                                                       OCH.sub.2CCH  166-167                                      CH.sub.3                                                                              C.sub.2 H.sub.5                                                                          OCH.sub.2CHCH.sub.2                                        CH.sub.3                                                                              CH(CH.sub.3).sub.2                                                                        ##STR26##    167-168                                      CH.sub.3                                                                              CH(CH.sub.3).sub.2                                                                        ##STR27##    141-142                                      CH.sub.3                                                                              CH(CH.sub.3).sub.2                                                                       OCH.sub.2CHCHCl                                            CH.sub.3                                                                              CH(CH.sub.3).sub.2                                                                       OCF.sub.2 CF.sub.2 H                                                                        124-126                                      CH.sub.3                                                                              CH(CH.sub.3).sub.2                                                                       OCH.sub.2 CHCHCH.sub.3                                                                      108-109                                      ______________________________________                                    

EXAMPLE 7 Preparation of2-(5-isopropyl-5-methyl-4-oxo-2-imidazolin-2-yl)-6-(2-propynyloxy)nicotinicacid ##STR28##

To a 100 mL propargyl alcohol at 5° C. under nitrogen is addedportionwise, with stirring and cooling, 1.44 g of a 50% suspension NaHin mineral oil. The resulting solution is added to 3.11 g of thechloropyridine and the mixture heated under nitrogen, on the steam bathfor 16 hours. The mixture is concentrated in vacuo, 100 mL toluene addedand again concentrated. The residue is dispersed in 100 mL water andextracted with 2×100 mL CH₂ Cl₂. The aqueous phase is cooled to 5° C.,acidified with H₂ SO₄ to pH 3 and extracted with 3×100 mL CH₂ Cl₂. Allthe organic extracts are combined, dried and concentrated to give aresidue consisting of a mixture of ester and acid.

The mixture is dissolved in 5 mL methanol, 5 mL 2N NaOH and 5 mL waterand stirred at room temperature for 16 hours. The mixture is extractedwith 50 mL ether, the aqueous phase acidified to pH 3 with H₂ SO₄ andextracted with 2×50 mL CH₂ Cl₂. The CH₂ Cl₂ extracts are combined, driedand concentrated. The residue is triturated with ether to give theproduct as a light orange solid which is recrystallized fromacetonitrile to give analytically pure2-(5-isopropyl-5-methyl-4-oxo-2-imidazolin-2-yl)-6-(2-propynyloxy)nicotinicacid. mp 195°-198° C.

Using essentially the same conditions but substituting the appropriatealcohol for propargyl alcohol, the following 6-substituted pyridines areprepared.

    ______________________________________                                         ##STR29##                                                                    R.sub.1 R.sub.2     Z             mp °C.                               ______________________________________                                        CH.sub.3                                                                              CH(CH.sub.3).sub.2                                                                        OCH.sub.2CHCH.sub.2                                                                         155-159                                     CH.sub.3                                                                              C.sub.2 H.sub.5                                                                           OCH.sub.2CHCH.sub.2                                       ______________________________________                                    

EXAMPLE 8 Preparation of7-(difluoromethoxy)-2-isopropyl-2-methyl-5H-imidazo[1'2':1,2]pyrrolo[3,4-b]pyridine-3(2H),5-dione ##STR30##

Dicyclohexylcarbodiimide (1.07 g, 5 mmol) in 20 mL CH₂ Cl₂ is added to astirred solution containing 1.54 g (4.7 mmol)5-(difluoromethoxy)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinicacid in 30 mL CH₂ Cl₂ under nitrogen at room temperature. The mixture isstirred overnight, filtered and concentrated to give the product,7-(difluoromethoxy)-2-isopropyl-2-methyl-5H-imidazo[1',2':1,2]pyrrolo[3,4-b]pyridine-3(2H),5-dione.

Using essentially the same conditions but substituting the appropriatesubstituted nicotinic acid for the difluoromethoxy derivative, thefollowing compounds are prepared.

    ______________________________________                                         ##STR31##                                                                    X    Y            Z            R.sub.1                                                                             R.sub.2                                  ______________________________________                                        H    OCF.sub.3    H            CH.sub.3                                                                            CH(CH.sub.3).sub.2                       H    OCF.sub.2 CHF.sub.2                                                                        H            CH.sub.3                                                                            CH(CH.sub.3).sub.2                       H    OCH.sub.2 CHCH.sub.2                                                                       H            CH.sub.3                                                                            CH(CH.sub.3).sub.2                       H    H            OCH.sub.2 CHCH.sub.2                                                                       CH.sub.3                                                                            CH(CH.sub.3).sub.2                       H    OCH.sub.2 CCH                                                                              H            CH.sub.3                                                                            CH(CH.sub.3).sub.2                       H    H            OCH.sub.2 CCH                                                                              CH.sub.3                                                                            CH(CH.sub.3).sub.2                       ______________________________________                                    

EXAMPLE 9 Preparation of7-alkyloxy-3-isopropyl-3-methyl-5H-imidazo[1',2':1,2]pyrrolo[3,4-b]pyridine-2-(3H),5-dione##STR32##

A solution containing 1.0 g 5-allyloxynicotinic acid and derivative in10 mL toluene containing 1 mL acetic anhydride is heated under refluxfor two hours. The solution is concentrated in vacuo to give the desiredpyridione.

Using essentially the same procedure but substituting the appropriatenicotinic acid for the 5-allyloxy derivatives, the following compoundsare prepared.

    ______________________________________                                         ##STR33##                                                                    X    Y             Z            R.sub.1                                                                            R.sub.2                                  ______________________________________                                        H    OCH.sub.2CH   H            CH.sub.3                                                                           CH(CH.sub.3).sub.2                             ##STR34##    H            CH.sub.3                                                                           CH(CH.sub.3).sub.2                       H                                                                                   ##STR35##    H            CH.sub.3                                                                           CH(CH.sub.3).sub.2                       H    H             OCH.sub.2 CHCH.sub.2                                                                       CH.sub.3                                                                           CH(CH.sub.3).sub.2                       H    OCHF.sub.2    H            CH.sub.3                                                                           CH(CH.sub.3).sub.2                       H    OCF.sub.3     H            CH.sub.3                                                                           CH(CH.sub.3).sub.2                       H    OCH.sub.2 CHCHCH.sub.3                                                                      H            CH.sub.3                                                                           CH(CH.sub.3).sub.2                       ______________________________________                                    

EXAMPLE 10 Preparation of methyl5-hydroxy-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinate-1-oxide##STR36##

A solution containing 10 g methyl5-hydroxy-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinate in100 mL acetic anhydride is heated under reflux for 16 hours. The mixtureis concentrated to give the crude diacetate which is dissolved in 125 mLmethylene chloride and 6.52 g m-chloroperbenzoic acid added. Afterheating and reflux for 16 hours, excess per acid is destroyed by theaddition of excess 1-hexane. The solution is washed with saturatedsodium bicarbonate solution, dried and concentrated. The residue isdissolved in 100 mL methanol and 2.0 g sodium methoxide added. Afterstirring for two hours, the pH of the solution is adjusted to 7 withacetic acid, the mixture concentration and the residue distributedbetween water and CH₂ Cl₂. The extract is dried and concentrated to givethe expected product, methyl5-hydroxy-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinate-1-oxide.

EXAMPLE 11 Preparation of methyl5-allyloxy-2-(4-isopropyl-4-methyl-5-thioxo-2-imidazolin-2-yl)nicotinate##STR37##

To a stirred suspension of 2.67 g P₂ S₅ in 18 mL dioxane is added 3.31 gof the ester and the mixture heated under reflux for 24 hours. Aftercooling to room temperature, the mixture is concentrated in vacuo and2.5 mL water added cautiously to the residue with stirring. The pH ofthe mixture is then adjusted to 8 with concentrated NH₄ OH whilstmaintaining a temperature of approximately 35° C. The mixture is cooledand extracted with CH₂ Cl₂, the extracts washed with water, dried andconcentrated to give methyl5-allyloxy-2-(4-isopropyl-4-methyl-5-thioxo-2-imidazolin-2-yl)nicotinate.

Using essentially the same procedure but reacting the appropriate 5-oxoderivative with P₂ S₅, the following compounds are prepared.

    ______________________________________                                         ##STR38##                                                                    R.sub.1                                                                             R.sub.2    Y              Z                                             ______________________________________                                        CH.sub.3                                                                            CH(CH.sub.3).sub.2                                                                       OCH.sub.2 CCH  H                                             CH.sub.3                                                                            CH(CH.sub.3).sub.2                                                                        ##STR39##     H                                             CH.sub.3                                                                            CH(CH.sub.3).sub.2                                                                       OCHF.sub.2     H                                             CH.sub.3                                                                            CH(CH.sub.3).sub.2                                                                        ##STR40##     H                                             CH.sub.3                                                                            CH(CH.sub.3).sub.2                                                                       CF.sub.2 CHF.sub.2                                                                           H                                             CH.sub.3                                                                            CH(CH.sub.3).sub.2                                                                       H              OCH.sub.2 CHCH.sub.2                          CH.sub.3                                                                            CH(CH.sub.3).sub.2                                                                       H              OCH.sub.2 CCH                                 CH.sub.3                                                                            C.sub.2 H.sub.5                                                                          OCH.sub.2 CHCH.sub.2                                                                         H                                             CH.sub.3                                                                            CH(CH.sub.3).sub.2                                                                       OCH.sub.2 CHCHCH.sub.3                                                                       H                                             ______________________________________                                         ##STR41##                                                                    L     M         Q       R.sub.7                                                                             R.sub.1                                                                              R.sub.2                                  ______________________________________                                        H     CHF.sub.2 H       H     CH.sub.3                                                                             CH(CH.sub.3).sub.2                       ______________________________________                                    

EXAMPLE 12

Preparation of 5-trifluoromethoxy-2-pyridinecarboxylic acid ##STR42##

A mixture of 3 g 5-trifluoromethoxy-2-pyridinemethanol is vigorouslystirred in 120 mL water at 5° C. To this mixture is added in severalportions 3.0 g potassium permanganate during which time the temperaturerises to 25° C. After a further 30 minutes at 25° C., the mixture isfiltered, the solid washed several times with water, the filtrate andwashings combined and the pH adjusted to 5. The solution is concentratedto a small volume and extracted with ethyl acetate several times. Theextract is washed, dried and concentrated to give5-trifluoromethoxy-2-pyridinecarboxylic acid.

EXAMPLE 13 Preparation of5-trifluoromethoxy-N-(1-carbamoyl-1,2-dimethylpropyl)picolinamide##STR43##

To a suspension of 2.31 g acid in 20 mL THF is added with stirring 1.07mL ethyl chloroformate. The mixture is cooled to -10° C. and 1.71 mLtriethylamine dropwise at such a rate that the temperature does notexceed 0° C. After ten minutes, a solution containing 1.43 g of2-amino-2,3-dimethylbutyramide in 15 mL THF is added dropwise at 0° C.with stirring. The mixture is stirred at room temperature for two hoursand enough water then added to dissolve the solids. The THF is removedin vacuo, the aqueous residue saturated with salt and extracted withethyl acetate. The organic phase is separated, dried and concentrated togive 5-trifluoromethoxy-N-(1-carbamoyl-1,2-dimethylpropyl)-picolinamide.

EXAMPLE 14 Preparation of2-(5-trifluoromethoxy-2-pyridyl)-4-isopropyl-4-methyl-2-imidazolin-5-one##STR44##

A stirred suspension of sodium hydride (0.24 g) in 25 mL toluene isheated under reflux under a Dean-Stark Water Separator. To this is addedin small portions 2.9 g diamide. After the addition, heating iscontinued for one and one half hours. After standing overnight, thereaction is quenched with water, the pH adjusted to 5 and the phasesseparated. The aqueous phase is further extracted with ethyl acetate,the organic phases combined, washed with brine, dried and concentratedto give the product2-(5-trifluoromethoxy-2-pyridyl)-4-isopropyl-4-methyl-2-imidazolin-5-one.

EXAMPLE 15 Preparation of5-trifluoromethoxy-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinicacid ##STR45##

To a stirred solution containing 1.1 g imidazolinone in 10 mL THF at-76° C. under nitrogen is added dropwise 4.7 mL of a 1.7M solution ofmethyl lithium in ether. An additional 15 mL THF containing 0.25 mLhexamethylphosphoramide is added. The mixture is allowed to warm to -20°to -10° C. and held at this temperature for 0.75 hours. The mixture iscooled to -70° C. and added to a slurry of carbon dioxide in THF. Afterstirring for 0.5 hours, water is added, the pH adjusted to 2 with dilutesulfuric acid and the mixture extracted with methylene chloride. Theextract is washed with brine, dried and concentrated to give theproduct,5-trifluoromethoxy-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinicacid.

By substituting the appropriate α-aminocarboxamide for this carboxamidein Example 12 the following trifluoromethoxynicotinic acids areobtained.

    ______________________________________                                         ##STR46##                                                                    R.sub.1       R.sub.2         W                                               ______________________________________                                        CH.sub.3      CH.sub.3 (CH.sub.3).sub.2                                                                     S                                               CH.sub.3      C.sub.2 H.sub.5 O                                               CH.sub.3      Cyclopropyl     O                                               CH.sub.3      CH.sub.3        O                                               CH.sub.3      C.sub.2 H.sub.5 S                                               ______________________________________                                    

EXAMPLE 16 Preparation of dimethyl3-p-difluoromethoxyphenylaminobut-2-ene-dioate ##STR47##

p-Difluoromethoxyaniline (0.217 mol) and dimethyl oxalacetate (0.217mol) are mixed in toluene (500 mL) and heated under reflux under aDean-Stark Water Separator for about one hour. The toluene is removed invacuo to give dimethyl 3-p-difluoromethoxyphenylaminobut-2-ene-dioate asan oil.

EXAMPLE 17 Preparation of dimethyl6-difluoromethoxyquinoline-2,3-dicarboxylate ##STR48##

To a solution of dimethylformamide (0.1 mol) in ethylenedichloride (100mL) cooled in an ice bath, is added dropwise, with stirring, phosphrousoxychloride (0.1 mol). The resulting solution is stirred at roomtemperature for one and one-half hours and then cooled again in an icebath. To this solution is added dropwise a solution of dimethyl3-p-difluoromethoxyphenylaminobut-2-ene-dioate (0.1 mol) in ethylenedichloride. The mixture is then heated under reflux for three hours,cooled and washed with half saturated brine. The organic phase isseparated, dried and concentrated to givedimethyl-6-difluoromethoxyquinoline-2,3-dicarboxylate, mp 84°-85° C.

EXAMPLE 18 Preparation of 6-difluoromethoxyquinoline-2,3-dicarboxylicacid ##STR49##

To a solution containing dimethyl6-difluoromethoxyquinoline-2,3-dicarboxylate (0.162 mol) in 150 mLethanol is added a solution of sodium hydroxide (0.5 mol) in 400 mLwater and the mixture heated at reflux for five hours. The ethanol isremoved in vacuo. The residue cooled to 5° C. and acidified withconcentrated HCl. The product is removed by filtration, washed withwater and dried to give 6-difluoromethoxyquinoline-2,3-dicarboxylic acidmp 226° C.

EXAMPLE 19 Preparation of 6-difluoromethoxyquinoline-2,3-dicarboxylicacid anhydride ##STR50##

A mixture of 6-difluoromethoxyquinoline-2,3-dicarboxylic acid (0.14 mol)in 125 mL acetic anhydride is heated at 85° C. for one-half hour andthen at 100° C. for one hour. The mixture is cooled, then filtered andthe solids washed with ether to give6-difluoromethoxyquinoline-2,3-dicarboxylic acid anhydride mp157.5°-158.5° C.

EXAMPLE 20 Preparation of6-difluoromethoxy-2-[(1-carbamoyl-1,2-dimethylpropyl)carbamoyl]-3-quinolinecarboxylicacid ##STR51##

A solution of 6-difluoromethoxyquinoline-2,3-dicarboxylic acid anhydride(0.037 mol) in 250 mL THF is stirred at 5° C. under nitrogen and asolution containing 2-amino-2,3-dimethylbutyramide (0.037 mol) in 50 mLTHF added dropwise. After stirring at room temperature for 17 hours, thesolvent is removed in vacuo to give the desired6-difluoromethoxy-2-[(1-carbamoyl-1,2-dimethylpropyl)-carbamoyl]-3-quinolinecarboxylicacid mp 194°-196° C.

EXAMPLE 21 Preparation of6-difluoromethoxy-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-3-quinolinecarboxylicacid ##STR52##

A solution of6-difluoromethoxy-2-[(1-carbamoyl-1,2-dimethylpropyl)-carbamoyl]-3-quinolinecarboxylicacid (0.0152 mol) in 50 mL water containing 0.06 mol sodium hydroxide isheated at 75°-80° C. for two hours. The solution is cooled to 5° C. andacidified with concentrated HCl. The precipitate is removed byfiltration, washed with water and air-dried to give6-difluoromethoxy-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-3-quinolinecarboxylicacid, mp 208°-209° C.

Following essentially the same procedures as described in Examples 8-13but using the appropriately substituted aniline fordifluoromethoxyaniline and the appropriate α-aminocarboxamide orα-aminothiocarboxamide for 2-amino-2,3-dimethylbutyramide, yields thecompounds illustrated below.

    __________________________________________________________________________     ##STR53##                                                                    R.sub.1                                                                          R.sub.2                                                                              L M      Q      R.sub.7                                                                            W mp °C.                                __________________________________________________________________________    CH.sub.3                                                                         CH(CH.sub.3).sub.2                                                                   H H      H      OCHF.sub.2                                                                         O                                              CH.sub.3                                                                         CH(CH.sub.3).sub.2                                                                   H H      OCHF.sub.2                                                                           H    O                                              CH.sub.3                                                                         C.sub.2 H.sub.5                                                                      H OCHF.sub.2                                                                           H      H    O                                              CH.sub.3                                                                         Cyclopropyl                                                                          H OCHF.sub.2                                                                           H      H    O                                              CH.sub.3                                                                         CH(CH.sub.3).sub.2                                                                   H H      OCF.sub.2 CHF.sub.2                                                                  H    O                                              CH.sub.3                                                                         CH(CH.sub.3).sub.2                                                                   H OCF.sub.2 CHF.sub.2                                                                  H      H    O                                              CH.sub.3                                                                         C.sub.2 H.sub.5                                                                      H OCF.sub.2 CHF.sub.2                                                                  H      H    O                                              CH.sub.3                                                                         CH(CH.sub.3).sub.2                                                                   H OCF.sub.3                                                                            H      H    O 207.0-210.0                                  CH.sub.3                                                                         CH(CH.sub.3).sub. 2                                                                  H OCHF.sub.2                                                                           H      H    S                                              __________________________________________________________________________

EXAMPLE 22 Postemergence Herbicidal Evaluation of Test Compounds

The postemergence herbicidal activity of the compounds of the presentinvention is demonstrated by the following tests, wherein a variety ofmonocotyledonous and dicotyledenous plants are treated with testcompounds dispersed in aqueous acetone mixtures. In the tests, seedlingplants are grown in jiffy flats for about two weeks. The test compoundsare dispersed in 50/50 acetone/water mixtures containing 0.5% TWEEN® 20,a polyoxyethylene sorbitan monolaurate surfactant of Atlas ChemicalIndustries, in sufficient quantity to provide the equivalent of about0.016 kg of 10 kg per hectare of active compound when applied to theplants through a spray nozzle operating at 40 psig for a predeterminedtime. After spraying, the plants are placed on greenhouse benches andare cared for in the usual manner, commensurate with conventionalgreenhouse practices. From four to five weeks after treatment, theseedling plants, are examined and rated according to the rating systemprovided below. The data obtained are recorded in Table XI below.

    ______________________________________                                                            % Difference in Growth                                    Rating System       from the Check                                            ______________________________________                                        0      No Effect         0                                                    1      Possible effect   1-10                                                 2      Slight effect    11-25                                                 3      Moderate effect  26-40                                                 5      Definite injury  41-60                                                 6      Herbicidal effect                                                                              61-75                                                 7      Good herbicidal effect                                                                         76-90                                                 8      Approaching complete kill                                                                      91-99                                                 9      Complete kill    100                                                   4      Abnormal growth, that is, a definite physiological                            malformation but with an over-all effect less than                            a 5 on the rating scale.                                               ______________________________________                                    

In most cases the data are for a single test, but in several instances,they are average values obtained from more than one test.

    ______________________________________                                        Plant Species Used                                                            ______________________________________                                        Barnyardgrass     (Echinochloa crusgalli)                                     Green foxtail     (Setaria viridis)                                           Purple Nutsedge   (Cyperus rotundus L.)                                       Wild Oats         (Avena fatua)                                               Quackgrass        (Agropyron repens)                                          Field Bindweed    (Convolvulus arvensis L.)                                   Cocklebur         (Xanthium pensylvanicum)                                    Morningglory      (Ipomoea purpurea)                                          Ragweed           (Ambrosia artemisiifolia)                                   Velvetleaf        (Abutilon theophrasti)                                      Barley            (Hordeum vulgare)                                           Corn              (Zea mays)                                                  Rice              (Oryza Sativa)                                              Soybean           (Glycine max)                                               Sunflower         (Helianthus annus)                                          Wheat             (Triticum aestivum)                                         ______________________________________                                    

    TABLE I      POST-EMERGENCE TESTS - RATES IN KG/HA   BARN FOX P NUT WILD QUACK FLD     MATRI MRN RAG VELVET SUGAR CORN  RICE, SOYBEAN Compound RATE YARDGR TAIL     SP SEDGE OATS GRASS BINDWD CARIA GLRY SP WEED LEAF BEETS FIELD COTTON     NATO BR       6-(Difluoromethoxy)- 1.000  9.0 9.0 0.0 9.0 7.0 9.0 8.0 9.0 9.0 4.0     9.0 9.0 9.0 7.0 3.0 2-(4-isopropyl-4- .500 8.0 9.0 0.0 9.0 4.0 4.0 6.0     8.0  3.0 9.0 9.0 7.0 6.0 1.0 methyl-5-oxo-2- .250 8.0 9.0 0.0 9.0 4.0     1.0 5.0 7.0  1.0 9.0 9.0 9.0 5.0 1.0 imidazolin-2-yl)-3- .125 6.0 7.0     0.0 8.0 1.0  2.0 6.0  1.0 9.0 9.0 9.0 4.0 1.0 quinolinecarboxylic .063     5.0 5.0 0.0 6.0 1.0 0.0 0.0 4.0  0.0 9.0 9.0 7.0 2.0 0.0 acid .032 1.0     4.0 0.0 6.0 0.0 0.0 0.0 1.0 3.0 0.0 7.0 7.0 6.0 1.0 0.0 6-(Trifluorometho     xy)- 1.000  3.0 9.0 0.0 9.0 7.0 0.0 6.0 4.0 9.0 0.0 9.0 9.0 2.0 7.0 3.0     2-(4-isopropyl-4- .500 1.0 9.0 0.0 9.0   4.0 2.0 9.0 0.0 9.0 9.0 1.0 7.0     2.0 methyl-5-oxo-2- .250 1.0 9.0 0.0 9.0 6.0 0.0 4.0 0.0 8.0 0.0 9.0 9.0     1.0 6.0 2.0 imidazolin-2-yl)-3- .125 0.0 6.0 0.0 8.0 4.0 0.0 2.0 0.0 6.0     0.0 9.0 9.0 0.0 4.0 2.0 quinolinecarboxylic 0.63 0.0 6.0 0.0 7.0 2.0 0.0     0.0 0.0 0.0 0.0 9.0 9.0 0.0 2.0 1.0 acid .032 0.0  0.0 4.0 2.0 0.0 0.0     0.0 0.0 0.0 7.0 6.0 0.0 2.0 1.0 2-(4-Isopropyl-4- 1.000  9.0 9.0 7.0 9.0     7.0 7.0 8.0 9.0 8.0 9.0 9.0 9.0 8.0 9.0 8.0 methyl-5-oxo-2-imida- .500     9.0 9.0 7.0 9.0 6.0  8.0 9.0 7.0 7.0 9.0 8.0 8.0 7.0 8.0 zolin-2-yl)-6-(2     -pro- .250 9.0 9.0 6.0 7.0 6.0 4.0 6.0 9.0 3.0 6.0 9.0 8.0 8.0 7.0 7.0     pynyl-oxy)nicotinic .125 8.0 8.0 6.0 7.0 6.0 3.0 3.0 7.0 2.0 3.0 9.0 7.0     8.0 7.0 6.0 acid .063 3.0 6.0 2.0 7.0 4.0 1.0 1.0 6.0 1.0 2.0 8.0 7.0     8.0 6.0 4.0  .032 1.0 4.0 1.0 3.0 1.0 0.0 0.0 3.0 0.0 0.0 4.0 4.0 4.0     4.0 2.0 6-(Allyloxy)-2-(4- 1.000  9.0 9.0 7.0 9.0 9.0 7.0 6.0 9.0 9.0     9.0 9.0 9.0 9.0 8.0 7.0 isopropyl-4-methyl- .500 9.0 9.0 7.0 9.0 9.0 7.0     6.0 9.0 4.0 9.0 9.0 9.0 9.0 9.0 7.0 5-oxo-2-imidazolin- .250 7.0 9.0 4.0     9.0 9.0 6.0 2.0 9.0 2.0 9.0 9.0 9.0 9.0 6.0 5.0 2-yl)nicotinic acid .125     3.0 9.0 4.0 9.0 9.0  2.0 9.0 1.0 5.0 9.0 9.0 9.0 5.0 5.0  .063 1.0 2.0     2.0 9.0 3.0 2.0 0.0 9.0 0.0 2.0 8.0 9.0 9.0 4.0 4.0  .032 0.0 0.0 0.0     6.0 0.0 0.0 0.0 8.0 0.0 0.0 8.0 7.0 7.0 3.0 3.0 Methyl 6-(allyloxy)-     1.000  8.0 9.0 6.0 9.0 7.0 7.0 8.0 7.0 4.0 7.0 9.0 7.0 6.0 9.0 4.0     2-(4-isopropyl-4- .500 4.0 8.0 5.0 8.0 4.0 2.0 2.0 6.0 3.0 6.0 9.0 7.0     5.0 5.0 3.0 methyl-5-oxo-2-imida- .250 2.0 6.0 3.0 4.0 3.0 1.0 0.0 3.0     2.0 2.0 7.0 5.0 2.0 3.0 2.0 zolin-2-yl)nicotinate .125 0.0 2.0 1.0 3.0     1.0 0.0 0.0 0.0 0.0 0.0 4.0 3.0 0.0 2.0 1.0  .063 0.0 0.0 0.0 2.0 0.0     0.0 0.0 0.0 0.0 0.0 2.0 2.0 0.0 1.0 0.0  .032 0.0 0.0 0.0 0.0 0.0 0.0     0.0 0.0 0.0 0.0 2.0 2.0 0.0 1.0 0.0 5-(Allyloxy)-2-(4-iso- 1.000  9.0     9.0 2.0 9.0 9.0 9.0 8.0 9.0 9.0 9.0 9.0 9.0 9.0 7.0 6.0 propyl-4-methyl-5     -oxo- .500 9.0 9.0 1.0 9.0 9.0 9.0 7.0 9.0 9.0 9.0 9.0 9.0 9.0 6.0 3.0     2-imidazolin-2-yl)- .250 8.0 9.0 1.0 9.0 9.0 9.0 3.0 7.0 7.0 7.0 9.0 9.0     9.0 4.0 3.0 nicotinic acid .125 8.0 9.0 1.0 9.0 9.0 9.0 3.0 7.0 5.0 6.0     7.0 9.0 9.0  3.0  .063 7.0 9.0 0.0 9.0 9.0 9.0 0.0 5.0 2.0 4.0 7.0 9.0     9.0 4.0 2.0  .032 4.0 8.0 0.0 7.0 5.0 8.0 0.0 2.0 0.0 2.0 7.0 9.0 2.0     3.0 2.0 Methyl 5-(allyloxy)-2- 1.000  8.0 9.0 0.0 9.0 9.0 9.0 7.0 9.0     9.0 7.0 9.0 9.0 9.0 7.0 6.0 (4-isopropyl-4-methyl- .500 7.0 8.0 0.0 6.0     9.0 9.0 5.0 7.0 7.0 4.0 9.0 9.0 9.0 7.0 6.0 5-oxo-2-imidazolin-2- .250     3.0 7.0 0.0 3.0 9.0 9.0 0.0 8.0 2.0 2.0 9.0 9.0 9.0 5.0 5.0 yl)nicotinate      .125 1.0 5.0 0.0 1.0 9.0 9.0 0.0 0.0 1.0 1.0 8.0 6.0 7.0 3.0 3.0  .063     0.0 4.0 0.0 0.0 2.0 2.0 0.0 0.0 0.0 0.0 7.0 3.0 6.0 2.0 2.0  .032 0.0     2.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 4.0 2.0 3.0 2.0 1.0 5-(Difluoromethox     y)-2- 1.000  9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 8.0 9.0     (4-isopropyl-4-methyl- .500 9.0 9.0 7.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0     9.0 9.0 8.0 8.0 5-oxo-imidazolin-2- .250 9.0 9.0 7.0 9.0 9.0 9.0 9.0 9.0     9.0 9.0 9.0 9.0 9.0 8.0 9.0 yl)nicotinic acid .125 9.0 9.0 6.0 9.0 9.0     7.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 8.0 6.0  .063 9.0 9.0 6.0 9.0 9.0 9.0     9.0 9.0 8.0 9.0 9.0 9.0 9.0 8.0 7.0  .032 9.0 9.0 5.0 9.0 9.0 9.0 7.0     9.0 4.0 9.0 9.0 9.0 9.0 7.0 3.0 Methyl 2-(4-isopro- 1.000  9.0 9.0 6.0     9.0 9.0 9.0 8.0 9.0 7.0 9.0 9.0 9.0 8.0 8.0 7.0 pyl-4-methyl-5-oxo- .500     8.0 9.0 3.0 9.0 9.0 9.0 6.0 9.0 5.0 7.0 9.0 9.0 9.0 7.0 5.0 2-imidazolin-     2-yl)- .250 5.0 9.0 1.0 9.0 5.0 9.0 6.0 9.0 3.0 5.0 9.0 9.0 9.0 7.0 3.0     5-(2-propynyloxy)- .125 5.0 9.0 1.0 6.0 3.0 9.0 3.0 4.0 2.0 3.0 9.0 9.0     7.0 6.0 3.0 nicotinate .063 0.0 8.0 0.0 0.0 0.0 8.0 0.0 2.0 0.0 0.0 6.0     8.0 7.0 5.0 2.0  .032 0.0 7.0 0.0 0.0 0.0 7.0 0.0 0.0 0.0 0.0 8.0 5.0     6.0  1.0 2-(4-Isopropyl-4- 1.000  9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0     9.0 9.0 9.0 9.0 9.0 8.0 methyl-5-oxo-2-imida- .500 9.0 9.0 9.0 9.0 9.0     9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 7.0 zolin-2-yl)-5-(2-pro- .250 9.0     9.0 9.0 9.0 9.0 9.0 9.0 9.0 8.0 9.0 9.0 9.0 8.0 9.0 6.0 pynyloxy)nicotini     c .125 9.0 9.0 6.0 9.0 8.0 9.0 9.0 9.0 6.0 9.0 9.0 9.0 9.0 9.0 6.0 acid     .063 9.0 9.0 3.0 9.0 8.0 9.0 5.0 9.0 6.0 9.0 9.0 9.0 5.0 8.0 4.0  .032     9.0 9.0 0.0 9.0 5.0 9.0 2.0 8.0 2.0 6.0 9.0 9.0  8.0 2.0 2-(4-Isopropyl-4     - 1.000       9.0  1.5 9.0 8.5 9.0 9.0 8.5  9.0 9.0 9.0 8.0  1.0 methyl-5-oxo-2-imi-     .500 8.5  0.5 9.0 8.5 9.0 8.5 5.5  9.0 9.0 9.0 8.0  0.0 dazolin-2-yl)-5-     .250 6.0  0.0 7.5 7.5 9.0 4.5 3.5  9.0 7.5 9.0 6.0  0.0 [(2-methylallyl)o     xy]- .125 3.0  0.0 6.5 7.5 9.0 3.5 2.0  9.0 5.5 9.0 4.0  0.0 nicotinic     acid .063 1.5  0.0 3.0 2.0 9.0 0.5 1.0  2.5 3.0 6.0 1.0  0.0  .032 0.0     0.0 1.0 0.0 8.0 0.0 0.0  0.0 2.0 4.0 0.5  0.0 Methyl 2-(4-isopro- 1.000     0.0  0.0 2.0 8.0 9.0 4.0 4.0  7.0 0.0 3.0 3.0 pyl-4-methyl-5-oxo- .500     0.0  0.0 2.0 6.0 9.0 3.0 2.0  8.0 0.0 3.0 3.0 2-imidazolin-2-yl)- .250     0.0  0.0 2.0 2.0 9.0 3.0 1.0  2.0 0.0 1.0 3.0 5-[(2-methylallyl)- .125     0.0  0.0 0.0 0.0 9.0 2.0 0.0  0.0 0.0 2.0 1.0 oxy]nicotinate 0.63 0.0     0.0 0.0 0.0 4.0 0.0 0.0  0.0 0.0 0.0 0.0  .032 0.0  0.0 0.0 0.0 0.0 0.0     0.0  0.0 0.0 0.0 0.0 5-(Butenyloxy)-2- 1.000  9.0  7.0 9.0 9.0 9.0 7.0     6.0 8.0 9.0 9.0 9.0 6.0  3.0 (4-isopropyl-4-methyl- .500 9.0  4.0 9.0     9.0 9.0 4.0 4.0 4.0 9.0 9.0 9.0 6.0  1.0 5-oxo-2-imidazolin-2- .250 6.0     1.0 9.0 8.0 9.0 0.0 2.0 2.0 9.0 9.0 9.0 2.0  1.0 yl)nicotinic acid .125     3.0  1.0 9.0 2.0 9.0 0.0 0.0 0.0 4.0 9.0 9.0 2.0  1.0  .063 0.0  1.0 9.0     2.0 8.0 0.0 0.0 0.0 4.0 9.0 7.0 0.0  0.0  .032 0.0  0.0 6.0 0.0 8.0 0.0     0.0 0.0 0.0 9.0 4.0 0.0  0.0 Methyl 5-[(2-chloro- 1.000  7.0  0.0 8.0     0.0 9.0  7.0 6.0 9.0 9.0 8.0 7.0  2.0 alkyl)oxy]-2-(4-iso- .500 4.0  0.0     6.0 6.0 9.0 8.0 4.0 2.0 8.0 4.0 7.0 2.0  0.0 propyl-4-methyl-5- .250 1.0      0.0 2.0 2.0 9.0 0.0 2.0 0.0 6.0 2.0 4.0 0.0  0.0 oxo-2-imidazolin-2-     .125 0.0  0.0 2.0 0.0 8.0 0.0 0.0 0.0 2.0 1.0 2.0 0.0  0.0 yl)nicotinate     .063 0.0  0.0 0.0 0.0 4.0 0.0 0.0 0.0 0.0 0.0 2.0 0.0  0.0  .032 0.0     0.0 0.0 0.0  0.0 0.0 0.0 0.0 0.0 2.0 0.0  0.0 5-[(2-chloroallyl)- 1.000     9.0  4.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 8.0  3.0 oxy]-2-(4-isopropyl     - .500 9.0  6.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 8.0  2.0 4-methyl-5-o     xo-2- .250 9.0  4.0 9.0 9.0 9.0 9.0 8.0 9.0 9.0 9.0 9.0 9.0  1.0     imidazolin-2-yl)- .125 6.0  2.0 9.0 4.0 9.0 6.0 4.0 6.0 9.0 9.0 9.0 7.0     1.0 nicotinic acid .063 2.0  2.0 8.0 2.0 9.0 2.0 4.0  8.0 9.0 9.0 3.0     0.0  .032 0.0  0.0 7.0 0.0 9.0 0.0 0.0 0.0 4.0 4.0 8.0 2.0  0.0

EXAMPLE 23 Preemergence Herbicidal Evaluation of Test Compounds

The preemergence herbicidal activity of the compounds of the presentinvention is exemplified by the following tests in which the seeds of avariety of monocotyledonous and dicotyledonous plants are separatelymixed with potting soil and planted on top of approximately one inch ofsoil in separate pint cups. After planting, the cups are sprayed withthe selected aqueous acetone solution containing test compound insufficient quantity to provide the equivalent of about 0.016 to 10 kgper hectare of test compound per cup. The treated cups are then placedon greenhouse benches, watered and cared for in accordance withconventional greenhouse procedures. From four to five weeks aftertreatment, the tests are terminated and each cup is examined and ratedaccording to the rating system set forth above. The herbicidalproficiency of the active ingredients of the present invention isevident from the test results which are recorded in Table XII below.Where more than one test is involved for a given compound, the data areaveraged.

    TABLE II      PRE-EMERGENCE TESTS - RATES IN KG/HA   BARN FOX P NUT WILD QUACK FLD     MATRI MRN RAG VELVET SUGAR CORN  RICE, SOYBEAN Compound RATE YARD GR     TAIL SP SEDGE OATS GRASS BINDWD CARIA GLRY SP WEED LEAF BEETS FIELD     COTTON NATO BR       6-(Difluoromethoxy)- .500 2.0 9.0 0.0 9.0 9.0 6.0 4.0 5.0 8.0 4.0 9.0     9.0 9.0 9.0 3.0 2-(4-isopropyl-4- .250 0.0 9.0 0.0 7.0 8.0 5.0 1.0 2.0     6.0 1.0 9.0 9.0 9.0 9.0 methyl-5-oxo-2- .125 0.0 9.0 0.0 7.0 8.0 3.0 0.0     1.0  0.0 9.0 9.0 0.0 7.0 imidazolin-2-yl)-3- .063 0.0 3.0 0.0 6.0 7.0     1.0 0.0 0.0  0.0 9.0 3.0 0.0 6.0 0.0 quinolinecarboxylic .032 0.0 0.0     0.0 3.0 5.0 0.0 0.0 0.0 0.0 0.0 9.0 1.0 0.0 0.0 0.0 acid .016 0.0 0.0     0.0 1.0 0.0 0.0 0.0 0.0 0.0 0.0 6.0 0.0 0.0 0.0 0.0 6-(Trifluoromethoxy)-      .500 9.0 9.0 2.0 9.0 9.0 9.0 9.0 9.0 9.0 8.0 9.0 9.0 9.0 9.0 3.0     2-(4-isopropyl-4- .250 5.0 8.0 1.0 9.0 9.0 9.0 8.0 9.0 9.0 7.0 9.0 9.0     9.0 9.0 3.0 methyl-5-oxo-2- .125 4.0 9.0 0.0 9.0 9.0 7.0 8.0 8.0 9.0 5.0     9.0 9.0 5.0 8.0 3.0 imidazolin-2-yl)-3- .063 0.0 8.0 0.0 6.0 7.0 2.0 6.0     6.0 9.0 3.0 9.0 9.0 2.0 6.0 2.0 quinolinecarboxylic .032 0.0 1.0 0.0 4.0     6.0 1.0 4.0 5.0  2.0 9.0 8.0 1.0 2.0 1.0 acid .016 0.0 0.0 0.0 1.0 2.0     0.0 1.0 1.0  1.0 8.0 8.0 0.0 1.0 0.0 2-(4-Isopropyl-4- .500 7.0 9.0 9.0     9.0 9.0 9.0 3.0 9.0 9.0 7.0 9.0 9.0 9.0 9.0 8.0 methyl-5-oxo-2-imida-     .250 5.0 8.0 9.0 9.0 9.0 9.0  9.0 9.0 7.0 9.0 9.0 9.0 9.0 5.0 zolin-2-yl)     -6-(2-pro- .125 2.0 6.0 8.0 3.0 9.0 6.0 0.0 4.0 4.0 5.0 9.0 6.0 6.0 8.0     3.0 pynyl-oxy)nicotinic .063 0.0 1.0 7.0 1.0 2.0 5.0 0.0 4.0 4.0 2.0 8.0     3.0 2.0 3.0 1.0 acid .032 0.0 0.0 0.0 0.0 1.0 0.0 0.0 1.0  0.0 7.0 1.0     1.0 2.0 1.0  .016 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 7.0 0.0 0.0     0.0 0.0 6-(Allyloxy)-2-(4- .500 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0     9.0 9.0 9.0 9.0 7.0 isopropyl-4-methyl- .250 4.0 9.0 9.0 9.0 9.0 8.0 4.0     9.0 9.0 8.0 9.0 9.0 9.0 9.0 5.0 5-oxo-2-imidazolin- .125 4.0 7.0 9.0 8.0     8.0 9.0 2.0 9.0 6.0 8.0 9.0 6.0 9.0 9.0 4.0 2-yl)nicotinic acid .063 2.0     4.0 9.0 2.0 7.0 0.0 0.0 7.0 0.0 7.0 9.0 6.0 7.0 7.0 3.0  .032 0.0 4.0     4.0 0.0 2.0 0.0 0.0 2.0 0.0 4.0 8.0 3.0  4.0 2.0  .016 0.0 0.0 0.0 0.0     0.0 0.0 0.0 0.0 0.0 0.0 8.0 2.0 2.0 3.0 2.0 Methyl 6-(allyloxy)- .500     9.0 9.0 8.0 9.0 9.0 4.0 4.0 8.0 8.0 8.0 9.0 7.0 7.0 6.0 3.0 2-(4-isopropy     l-4- .250 9.0 8.0 6.0 8.0 7.0 2.0 1.0 7.0 0.0 7.0 9.0 5.0 4.0 3.0 2.0     methyl-5-oxo-2-imida- .125 6.0 7.0 4.0 4.0 3.0 1.0 0.0 4.0 0.0 5.0 9.0     3.0 2.0 3.0 2.0 zolin-2-yl)nicotinate .063 2.0 3.0 2.0 1.0 1.0 0.0 0.0     1.0 0.0 2.0 9.0 2.0 2.0 2.0  .032 1.0 1.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0     1.0 9.0 2.0 1.0 0.0 2.0  .016 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0     4.0 2.0 1.0 0.0 2.0 5-(Allyloxy)-2-(4-iso- .500 9.0 9.0 8.0 9.0 9.0 9.0     8.0 8.3 9.0 9.0 9.0 9.0 8.7 9.0 propyl-4-methyl-5-oxo- .250 8.7 9.0 7.0     8.0 9.0 9.0 8.0 8.0 5.0 9.0 9.0 9.0 7.3 9.0 0.0 2-imidazolin-2-yl)- .125     8.0 7.0 6.0 7.0 9.0 9.0 4.0 7.3 7.0 8.0 9.0 9.0 4.7 8.0 1.0 nicotinic     acid .063 6.3 8.0 4.5 3.0 9.0 9.0 3.0 5.3 2.0 8.0 7.0 9.0 3.0* 9.0  .032     4.7* 7.0 0.5 1.0 5.0 7.5 1.0 0.7 1.0 6.0 9.0 6.0 4.0* 6.0  .016 2.7* 3.0     0.0 0.0 4.0 7.5 0.0 0.0 0.0 4.0 4.0 3.0 3.0* 3.0 0.0 Methyl 5-(allyloxy)-     2- .500 9.0 9.0 7.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 8.0 9.0 2.0     (4-isopropyl-4-methyl- .250 8.0 9.0 5.0 8.0 9.0 9.0 6.0 8.0 8.0 9.0 9.0     9.0  8.0 2.0 5-oxo-2-imidazolin-2- .125 7.0 9.0 2.0 6.0 7.0 9.0 6.0 4.0     6.0 9.0 9.0 9.0 3.0 9.0 0.0 yl)nicotinate .063 5.0 8.0 1.0 2.0  8.0 4.0     2.0 5.0 7.0 7.0 8.0  8.0 0.0  .032 2.0 3.0 0.0 1.0 0.0 6.0 0.0 0.0 0.0     3.0  3.0 0.0 3.0 0.0  .016 0.0 1.0 0.0 0.0 0.0 6.0 0.0 0.0 0.0 1.0 7.0     2.0 0.0 2.0 0.0 5-(Difluoromethoxy)-2- .500 9.0 9.0 9.0 9.0 9.0 9.0 9.0     9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 (4-isopropyl-4-methyl- .250 9.0 9.0 9.0     9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 5-oxo-2-imidazolin-2-     .125 8.0 9.0 9.0 9.0 9.0 9.0 8.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 7.0     yl)nicotinic acid .063 8.0 8.0 8.0 9.0 9.0 9.0 8.0 9.0 8.0 9.0 9.0 9.0     9.0 9.0 3.0  .032 6.0 9.0 9.0 9.0 9.0 9.0 6.0 9.0 8.0 8.0 9.0 9.0 9.0     7.0 5.0  .016 2.0 7.0 7.0 6.0 7.0 6.0 2.0 6.0 7.0 8.0 9.0 9.0 8.0 5.0     2.0 Methyl 2-(4-isopro- .500 9.0 9.0 9.0 9.0 9.0 9.0 9.0 8.0 8.0 9.0 9.0     9.0 9.0 9.0 3.0 pyl-4-methyl-5-oxo- .250 9.0 9.0 9.0 8.0 9.0 9.0 8.0 7.0     8.0 8.0 9.0 9.0 8.0 9.0 2.0 2-imidazolin-2-yl)- .125 8.0 9.0 8.0 2.0 7.0     9.0 2.0 4.0 5.0 8.0 9.0 9.0 7.0 9.0 2.0 5-(2-propynyloxy)- .063 7.0 8.0     8.0 0.0 5.0 9.0 0.0 4.0 5.0 8.0 9.0 9.0 7.0 6.0 2.0 nicotinate .032 7.0     6.0 5.0 0.0 3.0 9.0 0.0 0.0 0.0 6.0 8.0 2.0 3.0 6.0 1.0  .016 0.0 0.0     0.0 0.0 0.0 3.0 0.0 0.0 0.0 0.0 4.0 2.0 0.0 2.0 1.0 2-(4-Isopropyl-4-     .500 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0  9.0 6.0 methyl-5-ox     o-2-imida- .250 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 8.0 9.0 9.0 9.0 9.0     4.0 zolin-2-yl)-5-(2-pro- .125 8.0 9.0 9.0 8.0 9.0 9.0 8.0 7.0 7.0 8.0     9.0 9.0 8.0 9.0 3.0 pynyloxy)nicotinic .063 9.0 9.0 7.0 7.0 9.0 9.0 6.0     5.0 3.0 8.0 9.0 9.0 4.0 9.0 2.0 acid .032 7.0 6.0 6.0 0.0 9.0  0.0 2.0     0.0 7.0 9.0 7.0 4.0 7.0 2.0  .016   0.0  0.0 0.0 2-(4-Isopropyl-4- .500     9.0  3.0 7.5 9.0 9.0 7.0 8.0 8.0 8.5 9.0 8.0 8.5  1.0 methyl-5-oxo-2-imi-      .250 7.0  2.0 6.0 8.5 7.5 4.5 6.5 8.0 8.5 6.5 8.0 4.0  0.5 dazolin-2-yl)     -5- .125 4.5  0.5 3.0 4.0 4.0 3.0  5.0* 6.5 7.5 4.5 7.0 1.5  0.0     [(2-methylallyl)oxy]- .063 1.5  0.0 1.0 1.5 2.0 1.5 2.5 3.0 5.5 2.0 3.5     1.0  0.0 nicotinic acid .032 0.5  0.0 1.0 0.0 1.0 0.0 0.0 1.0 2.0 1.0     2.5 0.0  0.0  .016 0.0  0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 2.5 0.0  0.0     Methyl 2-(4-isopro- .500 9.0  2.0 4.0 8.0 8.0 9.0 6.0 8.0 8.0 8.0 7.0     3.0  2.0 pyl-4-methyl-5-oxo- .250 6.0  1.0 2.0 7.0 6.0 5.0 8.0 7.0 3.0     4.0 5.0 2.0  2.0 2-imidazolin-2-yl)- .125 2.0  0.0 1.0 6.0 4.0 2.0 4.0     2.0 1.0 3.0 3.0 0.0  1.0 5-[(2-methylallyl)- .063 0.0  0.0 0.0 2.0 2.0     0.0 0.0 2.0 0.0 3.0 2.0 0.0  0.0 oxy]nicotinate .032 0.0  0.0 0.0 0.0     0.0 0.0 0.0 0.0 0.0 0.0 2.0 0.0  0.0  .016 0.0  0.0 0.0 0.0 0.0 0.0 0.0     0.0 0.0 0.0 0.0 0.0  0.0 5-(2-Butenyloxy)-2- .500 9.0  4.0 7.0 9.0 9.0     2.0 4.0 6.0 7.0 9.0 9.0 6.0  0.0 (4-isopropyl-4-methyl- .250 7.0  2.0     5.0 7.0 8.0 1.0 2.0 4.0 5.0 7.0 7.0 2.0  0.0 5-oxo-2-imidazolin-2- .125     3.0  0.0 3.0 5.0 4.0 0.0 0.0 4.0 4.0 3.0 5.0 0.0  0.0 yl)nicotinic acid     .063 0.0  0.0 2.0 2.0 0.0 0.0 0.0 2.0 0.0 2.0 3.0 0.0  0.0  .032 0.0     0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 2.0 0.0  0.0  .016 0.0  0.0 0.0 0.0     0.0 0.0 0.0 0.0 0.0 0.0 2.0 0.0  0.0 Methyl 5-[(2-chloro- .500 9.0  0.0     6.0 9.0 9.0 8.0 6.0 8.0 9.0 8.0 8.0 7.0  3.0 alkyl)oxy]-2-(4-iso- .250     8.0  0.0 2.0 9.0 9.0 7.0 4.0 8.0 6.0 9.0 5.0 1.0  0.0 propyl-4-methyl-5-     .125 7.0  0.0 2.0 7.0 9.0 5.0 2.0 2.0 3.0 5.0 2.0 1.0  0.0 oxo-2-imidazol     in-2- .063 3.0  0.0 1.0 5.0 6.0 3.0 0.0 2.0 3.0 5.0 1.0 0.0  0.0     yl)nicotinate .032 0.0  0.0 0.0 4.0 4.0 0.0 0.0 0.0 2.0 4.0 0.0 0.0  0.0      .016 0.0  0.0 0.0 2.0 2.0 0.0 0.0 0.0 0.0 2.0 0.0 0.0  0.0 5-[(2-chloroa     llyl)- .500 9.0  2.0 9.0 9.0 9.0 8.0 9.0 9.0 9.0 9.0 8.0 7.0  1.0     oxy]-2-(4-isopropyl- .250 9.0  4.0 7.0 9.0 9.0 8.0 8.0 9.0 8.0 8.0 8.0     3.0  1.0 4-methyl-5-oxo-2- .125 6.0  0.0 4.0 4.0 7.0 4.0 3.0 4.0 5.0 5.0     5.0 1.0  0.0 imidazolin-2-yl)- .063 2.0  0.0 3.0  7.0 3.0 0.0 2.0 2.0     3.0 2.0 0.0  0.0 nicotinic acid .032 0.0  0.0 0.0 2.0 2.0 0.0 0.0 0.0     2.0 2.0 1.0 0.0  0.0  .016 0.0  0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 1.0     0.0  0.0

What is claimed is:
 1. A compound of the formula: ##STR54## wherein R₁is C₁ -C₄ alkyl;R₂ is C₁ -C₄ alkyl or C₃ -C₆ cycloalkyl; and when R₁ andR₂ are taken together with the carbon to which they are attached theymay represent C₃ -C₆ cycloalkyl optionally substituted with methyl; R ishydrogen; ##STR55## C₁ -C₁₂ alkyl optionally substituted with a memberselected from the group consisting of C₁ -C₃ alkoxy, halogen, hydroxy,C₃ -C₆ cycloalkyl, benzyloxy, furyl, phenyl, halophenyl,loweralkylphenyl, loweralkoxyphenyl, nitrophenyl, carboxyl,loweralkoxycarbonyl, cyano and triloweralkylammonium; C₃ -C₁₂ alkenyloptionally substituted with a member selected from the group consistingof C₁ -C₃ alkoxy, phenyl, halogen or loweralkoxycarbonyl or with two C₁-C₃ alkoxy groups or two halogen groups; C₃ -C₆ cycloalkyl optionallysubstituted with one or two C₁ -C₃ alkyl groups; C₃ -C₁₀ alkynyl; or acation; W is O or S; L, M, Q and R₇ each represent hydrogen, halogen, C₁-C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ alkylthio, C₁ -C₄ alkylsulfonyl, C₁ -C₄haloalkyl, difluoromethoxy, trifluoromethoxy, 1,1,2,2-tetrafluoroethoxy,NO₂, CN, phenyl, phenoxy, amino, C₁ -C₄ alkylamino, diloweralkylamino,chlorophenyl, methylphenyl, phenoxy substituted with one Cl, CF₃, NO₂ orCH₃ group, C₃ -C₈ straight or branched alkenyloxy optionally substitutedwith one to three halogens, or C₃ -C₈ straight or branched alkynyloxyoptionally substituted with one to three halogens; with the proviso thatat least one of L, M, Q or R₇, is difluoromethoxy, trifluoromethoxy,1,1,2,2-tetrafluoroethoxy, C₃ -C₈ straight or branched alkenyloxyoptionally substituted with one to three halogens, or C₃ -C₈ straight orbranched alkynyloxy optionally substituted with one to three halogens;the N-oxides thereof when W is O provided that R cannot be unsaturatedalkyl; the optical isomers thereof when R₁ and R₂ are not the same; thetautomers thereof; the acid addition salts thereof except when R is asalt-forming cation.
 2. A compound according to claim 1, wherein R, R₁,R₂ and W are as described in claim 1 and at least one of L, M, Q and R₇is difluoromethoxy, trifluoromethoxy, 1,1,2,2-tetrafluoroethoxy, OCH₂--CH═CH₂, OCH₂ --C.tbd.CH, ##STR56##
 3. The compound according to claim2,6-difluoromethoxy-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-3-quinolinecarboxylicacid.
 4. The compound according to claim 2,6-trifluoromethoxy-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-3-quinolinecarboxylicacid.
 5. The compound according to claim 2,6-(1,1,2,2-tetrafluoroethoxy)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-3-quinolinecarboxylicacid.
 6. A method for the control of monocotyledonous and dicotyledonousannual, perennial and aquatic plant species comprising: applying to thefoliage of said plants or to soil or water containing seeds or otherpropagating organs thereof, a herbicidally effective amount of acompound having a structure: ##STR57## wherein R₁ is C₁ -C₄ alkyl;R₂ isC₁ -C₄ alkyl or C₃ -C₆ cycloalkyl; and when R₁ and R₂ are taken togetherwith the carbon to which they are attached they may represent C₃ -C₆cycloalkyl optionally substituted with methyl; R is hydrogen, ##STR58##C₁ -C₁₂ alkyl optionally substituted with a member selected from thegroup consisting of: C₁ -C₃ alkoxy, halogen, hydroxy, C₃ -C₆ cycloalkyl,benzyloxy, furyl, phenyl, halophenyl, loweralkylphenyl,loweralkoxyphenyl, nitrophenyl, carboxyl, loweralkoxycarbonyl, cyano andtriloweralkylammonium; C₃ -C₁₂ alkenyl optionally substituted with amember selected from the group consisting of: C₁ -C₃ alkoxy, phenyl,halogen or loweralkoxycarbonyl or with two C₁ -C₃ alkoxy groups or twohalogen groups; C₃ -C₆ cycloalkyl optionally substituted with one or twoC₁ -C₃ alkyl groups; C₃ -C₁₀ alkynyl; or a cation; W is O or S; L, M, Qand R₇ each represent hydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁-C₄ alkylthio, C₁ -C₄ alkylsulfonyl, C₁ -C₄ haloalkyl, difluoromethoxy,trifluoromethoxy, 1,1,2,2-tetrafluoroethoxy, NO₂, CN, phenyl, phenoxy,amino, C₁ -C₄ alkylamino, diloweralkylamino, chlorophenyl, methylphenyl,phenoxy substituted with one Cl, CF₃, NO₂ or CH₃ group, C₃ -C₈ straightor branched alkenyloxy optionally substituted with one to threehalogens, or C₃ -C₈ straight or branched alkynyloxy optionallysubstituted with one to three halogens; with the proviso that at leastone of L, M, Q or R₇, is difluoromethoxy, trifluoromethoxy,1,1,2,2-tetrafluoroethoxy, C₃ -C₈ straight or branched alkenyloxyoptionally substituted with one to three halogens, or C₃ -C₈ straight orbranched alkynyloxy optionally substituted with one to three halogens;the N-oxides thereof when W is O provided that R cannot be unsaturatedalkyl; the optical isomers thereof when R₁ and R₂ are not the same; thetautomers thereof; the acid addition salts thereof except when R is asalt-forming cation.
 7. A method according to claim 6, wherein R₁, R₂,W, L, M, Q and R₇ are as described in said claim 6 and R is as describedin said claim 6, excepting that when R is a cation, it is an alkalimetal, alkaline earth metal, manganese, copper, iron, zinc, cobalt,lead, silver, nickel, ammonium or organic ammonium.
 8. The methodaccording to claim 6, comprising applying an effective amount of acompound wherein at least one of L, M, Q and R₇ is difluoromethoxy,trifluoromethoxy, 1,1,2,2-tetrafluoroethoxy, OCH₂ --CH═CH₂, OCH₂--C.tbd.CH, ##STR59##
 9. The method according to claim 6, wherein thecompound is6-difluoromethoxy-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-3-quinolinecarboxylicacid.
 10. The method according to claim 6, wherein the compound is6-trifluoromethoxy-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-3-quinolinecarboxylicacid.
 11. The method according to claim 6, wherein the compound is6-(1,1,2,2-tetrafluoroethoxy)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-3-quinolinecarboxylicacid.
 12. A compound according to claim 1, wherein R₁, R₂, W, L, M, Qand R₇ are as described in said claim 1, excepting that when R is acation, it is an alkali metal, alkaline earth metal, manganese, copper,iron, zinc, cobalt, lead, silver, nickel, ammonium or organic ammonium.